KR102457056B1 - curable compound - Google Patents

Abstract

A curable compound having good solvent solubility and capable of forming a cured product having super heat resistance is provided.
The sclerosing|hardenable compound of this invention is represented by following formula (1). In Formula (1), R< ¹ >, R< ² > represents a sclerosing|hardenable functional group, and D< ¹ >, D2 represents ^a single bond or a coupling group. L is a structure represented by the following formula (I) and a structure represented by the following formula (II) (wherein Ar ¹ to Ar ³ are a group excluding two hydrogen atoms from the structural formula of the aromatic ring, or two or more aromatic rings Represents a group excluding two hydrogen atoms from the structural formula bonded through a single bond or a linking group, X represents -CO-, -S- or -SO ₂ -, Y represents -S-, -SO ₂ -, -O- , -CO-, -COO- or -CONH-, n represents an integer of 0 or more).) represents a divalent group having a repeating unit.

Description

curable compound

The present invention relates to a curable compound, a curable composition containing the curable compound, a cured product thereof, and a molded product including the cured product. In particular, it relates to materials usable in fields requiring good processability and high heat resistance, including electronic information, home appliances, automobiles, and precision machines. This application claims the priority of PCT/CN2016/110302 for which it applied on December 16, 2016 with the Chinese Intellectual Property Office as the receiving office, and uses the content here.

Engineering plastics are high-performance materials that combine high heat resistance and high mechanical properties, and are being used as essential materials for miniaturization, weight reduction, high performance, and high reliability of various parts. However, for example, polyimide having excellent heat and environmental resistance and strength characteristics is poorly soluble and hardly soluble, so the molding method for obtaining a molded article according to the use is limited. Therefore, research and development to overcome difficult formability is being actively conducted, and materials that combine high mechanical properties, electrical properties, chemical resistance, water resistance, high heat resistance and good processability of engineering plastics, that is, composites used under harsh temperature environments. As a functional material such as a molding material, an insulating material, and a heat-resistant adhesive, there is a demand for a curable compound capable of forming a cured product having good solvent solubility and super heat resistance.

It is known that the aromatic polyimide described in Patent Document 1 and the like is excellent in heat resistance. However, since it is difficult to dissolve in a solvent, workability is insufficient, and it is difficult to perform melt molding or use it as a matrix resin of a fiber-reinforced composite material.

Non-patent document 1 describes that by using an asymmetric acid dianhydride, a sclerosing compound having high melt fluidity, high heat resistance, high toughness, and moldability is obtained. However, since it is hardly soluble in a solvent, it was a problem that it could not be used for the purpose of forming hardened|cured material by the casting method etc.

Non-patent document 2 describes that a crosslinkable polyether ketone having solubility in a solvent such as toluene is obtained by using a special monomer containing fluorine. However, since a special raw material is essential, it lacks versatility.

Non-patent document 3 describes that crosslinkable polyether ketone having solvent solubility is obtained using bisphenol A and bis(4-chlorobenzoyl)benzene or 4,4'-difluorobenzophenone as raw materials. However, the high molecular weight has poor processability, and when the molecular weight is reduced to improve processability, the resulting cured product becomes brittle.

Non-Patent Document 4 describes a curable compound in which an acetylene end group is introduced through an ester bond into an ether ketone oligomer composed of a combination of a metaphenylene unit and a paraphenylene unit. However, the problem was that the curable compound had crystallinity, had low solvent solubility, and that the thermal decomposition initiation temperature of the resulting cured product was also low.

Japanese Patent Laid-Open No. 2000-219741

「Network Polymer」, Vol. 27(4) 221-231 (2006) Polymer Journal Vol34(3) 209-218(2002) Polymer Vol. 30 978-985 (1989) Polymer Vol. 33 (15) 3286-3291 (1992)

Accordingly, an object of the present invention is to provide a curable compound capable of forming a cured product having good solvent solubility and superheat resistance or a curable composition containing the same.

Another object of the present invention is to provide a cured product having super heat resistance as a cured product of the curable composition.

Another object of the present invention is to provide a molded product including the cured product.

As a result of intensive studies of the present inventors in order to solve the above problems, the compound represented by the following formula (1) has good solvent solubility and is cured by applying an external stimulus such as heat to form a cured product having super heat resistance found out what to do This invention was completed based on these knowledge.

That is, this invention provides the sclerosing|hardenable compound represented by following formula (1).

[Wherein, R ¹ , R ² are the same or different and represent a curable functional group, and D ¹ , D ² are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit comprising a structure represented by the following formula (I) and a structure represented by the following formula (II).

(Wherein, Ar ¹ to Ar ³ are the same or different, and a group excluding two hydrogen atoms from the structural formula of an aromatic ring, or a group excluding two hydrogen atoms from a structural formula in which two or more aromatic rings are bonded through a single bond or a linking group X represents -CO-, -S- or -SO ₂ -, Y is the same or different, -S-, -SO ₂ -, -O-, -CO-, -COO- or -CONH represents -. n represents an integer greater than or equal to 0)]

This invention also provides the said sclerosing|hardenable compound whose R< ¹ >, R< ² > in Formula (1) is the same or different and is a sclerosing|hardenable functional group which has a cyclic imide structure.

The present invention also provides the above curable compound, wherein R ¹ and R ² in formula (1) are the same or different and are a group selected from groups represented by the following formulas (r-1) to (r-6). .

(In the formula, a bond extending from a nitrogen atom bonds with D ¹ or D ² )

In the present invention, D ¹ , D ² in formula (1) is the same or different, and the following formulas (d-1) to (d-4)

A group selected from a group including a structure represented by , provides the above curable compound.

The present invention also provides a group in which Ar ¹ to Ar ³ in formulas (I) and (II) are the same or different and excluding two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms, or a group having 6 to 14 carbon atoms At least two of the aromatic rings are a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a group in which at least one hydrogen atom of a linear or branched alkylene group having 1 to 5 carbon atoms is substituted with a halogen atom The group excluding two hydrogen atoms from the combined structural formula, provides the above curable compound.

This invention also provides the said sclerosing|hardenable compound whose structure represented by Formula (I) is a structure derived from benzophenone.

This invention also provides the said sclerosing|hardenable compound whose ratio which the structural unit derived from benzophenone in sclerosing|hardenable compound whole quantity represented by Formula (1) occupies is 5 weight% or more.

In the present invention, the structure represented by formula (II) is hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxybiphenyl, 4,4 '-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and bisphenol A It provides the said curable compound which is a structure derived from at least 1 sort(s) of compound.

This invention also provides the said curable compound whose ratio for which the structural unit derived from hydroquinone, resorcinol, and bisphenol A in the curable compound whole quantity represented by Formula (1) occupies is 5 weight% or more.

The present invention also provides a curable composition comprising the curable compound.

The present invention also provides a cured product of the curable composition. The present invention also provides a molded product comprising the cured product.

The curable compound of the present invention having the above structure (particularly, a molecular chain having a repeating unit comprising a structural unit derived from benzophenone and a structural unit derived from at least one compound selected from hydroquinone, resorcinol and bisphenol A) A compound having a specific curable functional group introduced at both ends) has good solvent solubility. Moreover, it can harden|cure quickly by heat-processing etc., and can form the hardened|cured material which has super heat resistance. In addition, these cured products have good dielectric properties (low dielectric constant and dielectric loss tangent). Therefore, the curable compound of this invention can be used suitably in the field|area in which favorable processability (or moldability) and high heat resistance are requested|required including electronic information, a home appliance, an automobile, and a precision machine.

1 is a view showing ¹ H-NMR spectrum (DMSO-d6) of diamine-2-1 and diamine-2-2 obtained in Preparation Examples 1 and 2.
FIG. 2 is a diagram showing an FTIR spectrum of diamine-2-1 obtained in Preparation Example 1. FIG.
3 is a view showing an FTIR spectrum of diamine-2-2 obtained in Preparation Example 2.
4 is a diagram showing ¹ H-NMR spectra (DMSO-d6) of diamine-1-1 and diamine-1-2 obtained in Production Examples 3 and 4. FIG.
5 is a view showing an FTIR spectrum of diamine-1-1 obtained in Production Example 3.
6 is a view showing an FTIR spectrum of diamine-1-2 obtained in Production Example 4.
7 is a diagram showing ¹ H-NMR spectra (CDCl ₃ ) of BEI-2-1 and BEI-2-2 obtained in Examples 1 and 2;
FIG. 8 is a diagram showing an FTIR spectrum of BEI-2-1 obtained in Example 1. FIG.
9 is a diagram showing an FTIR spectrum of BEI-2-2 obtained in Example 2. FIG.
10 is a diagram showing ¹ H-NMR spectra (CDCl ₃ ) of BEI-1-1 and BEI-1-2 obtained in Examples 3 and 4;
11 is a diagram showing an FTIR spectrum of BEI-1-1 obtained in Example 3. FIG.
12 is a diagram showing an FTIR spectrum of BEI-1-2 obtained in Example 4. FIG.
13 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ ) of BMI-2-1 obtained in Example 5;
14 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ ) of BMI-1-1 obtained in Example 6. FIG.
15 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP = 2/1) of BMI-1-2 obtained in Example 7. FIG.
16 is a diagram showing ¹ H-NMR spectrum/CDCl ₃ of BMI-2-2 obtained in Example 8).
FIG. 17 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP=2/1) of BMI-3 obtained in Example 9. FIG.
18 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP = 2/1) of BMI-4 obtained in Example 10. FIG.
19 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP = 2/1) of BMI-5 obtained in Example 11;
20 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP = 2/1) of BMI-6 obtained in Example 12. FIG.
21 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ ) of BMI-7 obtained in Example 13. FIG.
22 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP=2/1) of BMI-8 obtained in Example 14. FIG.
23 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ ) of BMI-9 obtained in Example 15. FIG.
Fig. 24 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP = 2/1) of BMI-10 obtained in Example 16;
Fig. 25 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ /PFP = 2/1) of BMI-1-3 obtained in Example 17;
26 is a diagram showing ¹ H-NMR spectrum (CDCl ₃ ) of BMI-1-4 obtained in Example 18. FIG.
Fig. 27 is a diagram showing an FTIR spectrum of BMI-3 obtained in Example 9;
28 is a diagram showing an FTIR spectrum of BMI-4 obtained in Example 10;
29 is a diagram showing an FTIR spectrum of BMI-5 obtained in Example 11;
30 is a diagram showing an FTIR spectrum of BMI-6 obtained in Example 12;
Fig. 31 is a diagram showing an FTIR spectrum of BMI-7 obtained in Example 13;
Fig. 32 is a diagram showing an FTIR spectrum of BMI-8 obtained in Example 14;
Fig. 33 is a diagram showing an FTIR spectrum of BMI-9 obtained in Example 15;
Fig. 34 is a diagram showing the FTIR spectrum of BMI-10 obtained in Example 16;
It is a figure which shows the DSC measurement result of the hardened|cured material of BMI-3 obtained in Example 9.
It is a figure which shows the DSC measurement result of the hardened|cured material of BMI-4 obtained in Example 10.
Fig. 37 is a diagram showing the results of DSC measurement of the cured product of BMI-5 obtained in Example 11;
Fig. 38 is a diagram showing the results of DSC measurement of a cured product of BMI-6 obtained in Example 12;
Fig. 39 is a diagram showing the results of DSC measurement of the cured product of BMI-7 obtained in Example 13;
Fig. 40 is a diagram showing the results of DSC measurement of the cured product of BMI-8 obtained in Example 14;
Fig. 41 is a diagram showing the results of DSC measurement of the cured product of BMI-9 obtained in Example 15;
Fig. 42 is a diagram showing the results of DSC measurement of the cured product of BMI-10 obtained in Example 16;
Fig. 43 is a diagram showing the DSC measurement results of BEI-2-1, BEI-2-2 and BEI-1-1 and BEI-1-2 obtained in Examples 1-4.
Fig. 44 is a diagram showing the DSC measurement results of the cured products of BEI-2-1, BEI-2-2 and BEI-1-1 and BEI-1-2 obtained in Examples 1-4.
45 is a diagram showing the results of analysis of thermogravimetric reduction of the cured products of BEI-2-1, BEI-2-2 and BEI-1-1 and BEI-1-2 obtained in Examples 1 to 4;
46 is a diagram showing an FTIR spectrum of BMI-1-2 obtained in Example 7. FIG.
47 is a diagram showing an FTIR spectrum of BMI-2-2 obtained in Example 8;
Fig. 48 is a diagram showing the results of the DSC measurement of BMI-1-2 obtained in Example 7.
Fig. 49 is a diagram showing the DSC measurement result of BMI-2-2 obtained in Example 8;

[Curable compound]

The sclerosing|hardenable compound of this invention is represented by following formula (1).

In Formula (1), R< ¹ >, R< ² > is the same or different, and represents a sclerosing|hardenable functional group, D< ¹ >, D2 is ^the same or different, and represents a single bond or a coupling group. L represents a divalent group having a repeating unit comprising a structure represented by the following formula (I) and a structure represented by the following formula (II).

(Wherein, Ar ¹ to Ar ³ are the same or different, and a group excluding two hydrogen atoms from the structural formula of an aromatic ring, or a group excluding two hydrogen atoms from a structural formula in which two or more aromatic rings are bonded through a single bond or a linking group X represents -CO-, -S- or -SO ₂ -, Y is the same or different, -S-, -SO ₂ -, -O-, -CO-, -COO- or -CONH represents -. n represents an integer greater than or equal to 0)

In formula, R< ¹ >, R< ² > represents a sclerosing|hardenable functional group. R ¹ , R ² may be the same or different from each other. As a sclerosing|hardenable functional group in R< ¹ >, R< ² >, for example, a sclerosing|hardenable functional group which has a cyclic imide structure, such as group represented by a following formula (r), is preferable.

(In the formula, a bond extending from a nitrogen atom bonds with D ¹ or D ² )

In the formula (r), Q represents C or CH. Qs may form a double bond. n' is an integer of 0 or more (eg 0 to 3, preferably 0 or 1). R ³ to R ⁶ are the same or different, and are a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group (preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms), An aromatic hydrocarbon group (preferably an aryl group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group) or a group in which two or more groups selected from the above saturated or unsaturated aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded. Two groups selected from R ³ to R ⁶ may be bonded to each other to form a ring together with adjacent carbon atoms.

Examples of the ring which two groups selected from R ³ to R ⁶ may be bonded to each other to form together with an adjacent carbon atom include an alicyclic ring having 3 to 20 carbon atoms and an aromatic ring having 6 to 14 carbon atoms. In the said C3-C20 alicyclic ring, for example, 3-20 membered (preferably 3-15 membered, Especially preferably 5-8 membered), such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, ) of cycloalkane rings; a cycloalkene ring having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as a cyclopentene ring and a cyclohexene ring; Crosslinking of perhydronaphthalene ring, norbornane ring, norbornene ring, adamantane ring, tricyclo[5.2.1.0 ^2,6 ]decane ring, tetracyclo[4.4.0.1 ^{2,5.1 7,10} ]dodecane ring A cyclic hydrocarbon group and the like are included. A benzene ring, a naphthalene ring, etc. are contained in the said C6-C14 aromatic ring.

As the curable functional group having a cyclic imide structure, among them, a curable functional group having a cyclic unsaturated imide structure or a curable functional group having a cyclic imide structure having an arylethynyl group is preferable, and particularly preferably the following formula ( It is a group selected from the group represented by r-1)-(r-6), Especially preferably, it is a group represented by a following formula (r-1) or (r-5).

(In the formula, a bond extending from a nitrogen atom bonds with D ¹ or D ² )

One or two or more substituents may be bonded to the groups represented by the formulas (r-1) to (r-6). Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

Examples of the alkyl group having 1 to 6 carbon atoms include linear groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group and hexyl group; and a branched alkyl group.

As said C1-C6 alkoxy group, linear or branched alkoxy groups, such as a methoxy group, an ethoxy group, a butoxy group, and t-butyloxy group, are mentioned, for example.

In formula (1), D ¹ and D ² are the same or different and represent a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a group in which a plurality of these bonds are linked.

The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group.

As said divalent aliphatic hydrocarbon group, a C1-C18 linear or branched alkylene group, a C2-C18 linear or branched alkenylene group, etc. are mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. As a C2-C18 linear or branched alkenylene group, a vinylene group, 1-methylvinylene group, propenylene group, 1-butenylene group, 2-butenylene group etc. are mentioned, for example.

Examples of the divalent alicyclic hydrocarbon group include a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, for example, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, Cycloalkylene groups (including a cycloalkylidene group), such as a 1,2-cyclohexylene group, a 1, 3- cyclohexylene group, a 1, 4- cyclohexylene group, and a cyclohexylidene group, etc. are mentioned.

Examples of the divalent aromatic hydrocarbon group include an arylene group having 6 to 14 carbon atoms, for example, a 1,4-phenylene group, a 1,3-phenylene group, a 4,4′-biphenylene group, 3,3'-biphenylene group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,8-naphthalenediyl group, anthracenediyl group, etc. are mentioned.

The heterocycle constituting the divalent heterocyclic group includes an aromatic heterocycle and a non-aromatic heterocycle. As such a heterocyclic ring, a 3 to 10 membered ring (preferably a 4 to 6 membered ring) having a carbon atom and at least one heteroatom (eg, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) in atoms constituting the ring. , and condensed rings thereof. Specifically, a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a three-membered ring such as an oxirane ring; a four-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, γ 5-membered rings such as -butyrolactone ring, 4-oxo-4H-pyran ring, tetrahydropyran ring, 6-membered ring such as morpholine ring, benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, Condensed rings such as chroman ring and isochroman ring: 3-oxatricyclo[4.3.1.1 ^4,8 ]undecan-2-one ring, 3-oxatricyclo[4.2.1.0 ^4,8 ]nonan-2-one ring, etc. of a heterocyclic ring containing a sulfur atom as a hetero atom (for example, a 5-membered ring such as a thiophene ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring; a 4-oxo-4H-thiopyran ring, etc.) 6-membered ring; 6-membered ring, such as isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring; indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline Condensed rings, such as a ring and a purine ring, etc.) etc. are mentioned. The divalent heterocyclic group is a group in which two hydrogen atoms are removed from the structural formula of the heterocycle.

Among them, D ¹ , D ² preferably contains a divalent aromatic hydrocarbon group from the viewpoint of obtaining a cured product having particularly excellent heat resistance. The divalent aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms, more preferably a group selected from the groups represented by the following formulas (d-1) to (d-4), particularly preferably Preferably, it is a group (1,2-phenylene group, 1,3-phenylene group, or 1,4-phenylene group) represented by the following formula (d-1).

The divalent aromatic hydrocarbon group may have at least one group selected from the group consisting of a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imide bond, and among them, it is preferable to have an ether bond do. In addition, the ether bond is preferably directly bonded to L. Therefore, the R ¹ -D ¹ - group and the R ² -D ² - group in the formula (1) are the same as or different from the following formulas (rd-1), (rd-2), (rd-3), or The group represented by (rd-4) is preferable, and the group represented by (rd-3) or (rd-4) is particularly preferable.

(In the formula, a bond growing from a phenylene group or an oxygen atom is bonded to L)

In formula (1), L represents a divalent group having a repeating unit comprising the structure represented by the formula (I) and the structure represented by the formula (II). That is, L represents a divalent group having a structure in which the structure represented by the formula (I) and the unit including the structure represented by the formula (II) are repeated twice or more. In formulas (I) and (II), Ar ¹ to Ar ³ are the same or different, and a group excluding two hydrogen atoms from the structural formula of the aromatic ring, or 2 from the structural formula in which two or more aromatic rings are bonded through a single bond or a linking group represents a group excluding hydrogen atoms. X represents -CO-, -S- or -SO ₂ -, Y is the same or different, -S-, -SO ₂ -, -O-, -CO-, -COO- or -CONH- indicates. n represents an integer of 0 or more, for example, an integer of 0 to 5, preferably an integer of 1 to 5, particularly preferably an integer of 1 to 3.

As said aromatic ring (= aromatic hydrocarbon ring), C6-C14 aromatic rings, such as benzene, naphthalene, anthracene, and a phenanthrene, are mentioned, for example. In this invention, C6-C10 aromatic rings, such as benzene and naphthalene, are especially preferable.

Examples of the linking group include a divalent hydrocarbon group having 1 to 5 carbon atoms and a group in which at least one hydrogen atom of a divalent hydrocarbon group having 1 to 5 carbon atoms is substituted with a halogen atom.

Examples of the divalent hydrocarbon group having 1 to 5 carbon atoms include a linear or branched alkylene group having 1 to 5 carbon atoms, such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group; a linear or branched alkenylene group having 2 to 5 carbon atoms, such as a vinylene group, a 1-methylvinylene group, and a propenylene group; and a linear or branched alkynylene group having 2 to 5 carbon atoms, such as an ethynylene group, a propynylene group, and 1-methylpropynylene. In this invention, a C1-C5 linear or branched alkylene group is especially preferable, and a C1-C5 branched alkylene group is especially preferable.

Accordingly, Ar ¹ to Ar ³ are the same or different, and a group excluding two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms, or two or more of an aromatic ring having 6 to 14 carbon atoms, a single bond, or 1 carbon number A group excluding two hydrogen atoms from the structural formula in which at least one hydrogen atom of a straight-chain or branched alkylene group having 1 to 5 carbon atoms or a straight-chain or branched chain alkylene group having 1 to 5 carbon atoms is substituted with a halogen atom is preferably a group and, in particular, a group excluding two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms, or two or more of an aromatic ring having 6 to 14 carbon atoms, a single bond, a branched chain alkylene group having 1 to 5 carbon atoms, or 1 to carbon atoms It is preferable that it is a group excluding two hydrogen atoms from the structural formula in which at least one hydrogen atom of the branched alkylene group of 5 is bonded through a group substituted with a halogen atom.

The Ar ¹ to Ar ³ are preferably the same or different and preferably a group selected from the groups represented by the following formulas (a-1) to (a-5). In addition, the attachment position of a bond in particular in the following formula is not restrict|limited.

Among them, as Ar ¹ and Ar ² in formula (I), a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms is preferable, and is particularly represented by the formula (a-1) or (a-2) A group that becomes Moreover, as X, -CO- or -SO ₂ - is especially preferable. As a structure represented by Formula (I), it is preferable especially that the structure derived from benzophenone is included.

The proportion of the structural unit derived from benzophenone in the total amount of the sclerosing compound represented by the formula (1) is, for example, 5% by weight or more, preferably 10 to 62% by weight, particularly preferably 15 to 60% by weight. %to be.

Among them, as Ar ³ in formula (II), a group selected from the groups represented by the formulas (a-1), (a-4) and (a-5) is preferable. Moreover, as Y, -S-, -O-, or -SO ₂ - is especially preferable. Examples of the structure represented by the formula (II) include hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxybiphenyl, and 4,4'-dihydro At least one selected from hydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylsulfone and bisphenol A It is preferred to include a structure derived from the compound.

The proportion of structural units derived from hydroquinone, resorcinol and bisphenol A in the total amount of the sclerosing compound represented by the formula (1) is, for example, 5% by weight or more, preferably 10 to 55% by weight, particularly Preferably it is 15 to 53 weight%.

Among these, L in formula (1) is preferably a divalent group represented by the following formula (l-1) from the viewpoint of obtaining a cured product having particularly excellent heat resistance, and is preferably a divalent group represented by the following formula (l-2) or (l-) It is more preferable that it is a divalent group represented by 3).

In the above formula, m1, m2, and m3 are the repeating units represented in round brackets included in the molecular chain (= the divalent group represented by the above formulas (l-1), (l-2) or (l-3)) The number, that is, the average degree of polymerization, is, for example, 2 to 50, preferably 3 to 40, more preferably 4 to 30, particularly preferably 5 to 20. When m1, m2, and m3 are less than 2, the intensity|strength of the hardened|cured material obtained becomes inadequate. In addition, the values of m1, m2, and m3 can be calculated|required by GPC measurement or NMR spectral analysis. In addition, n in Formula (1-1) is the same as that in Formula (II).

Since the curable compound of the present invention has the above structure, a cured product having a highly crosslinked structure (that is, a high crosslinking density) and having super heat resistance is obtained by curing reaction by heat or the like.

Moreover, since the sclerosing|hardenable compound of this invention has the said structure, it shows the outstanding solubility with respect to the following solvent.

Solvent: For example, aromatic hydrocarbons, such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and benzotrifluoride; esters such as ethyl acetate; ethers such as tetrahydrofuran; ketones such as cyclohexanone; N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, and mixtures thereof, and the like.

Further, among the curable compounds of the present invention, in the formula (1), L is a divalent group represented by the formula (1-2) or (1-3), in the formula, m2, m3 is 5 to 10 compounds, Since it melts at 300°C or less (about 250°C), it can be melt-molded at a low temperature compared to PEEK or the like, and is particularly excellent in moldability.

On the other hand, when the average degree of polymerization of a molecular chain is less than the said range, the hardened|cured material obtained becomes brittle, and there exists a tendency for a mechanical characteristic to fall. Moreover, when the average degree of polymerization of a molecular chain exceeds the said range, there exists a tendency for molding processability to fall by the solubility to a solvent falling, melt viscosity increasing, etc.

The sclerosing|hardenable compound represented by said Formula (1) can be manufactured using the synthesis method described in Polymer 1989 p978, for example. Although an example of the manufacturing method of the sclerosing|hardenable compound represented by the said Formula (1) is shown below, it is not limited to this manufacturing method in particular.

The compound represented by the following formula (1-1) can be produced through the following steps [1] to [3]. In the following formula, Ar ¹ to Ar ³ , X, Y, n, R ³ to R ⁶ , Q, and n′ are the same as above. D represents a linking group, and Z represents a halogen atom. n ³ is the average degree of polymerization of the repeating unit, and is, for example, 3 to 50, preferably 4 to 30, particularly preferably 5 to 20. Among the sclerosing|hardenable compounds represented by said Formula (1), compounds other than the compound represented by following formula (1-1) can also be manufactured according to the following method.

Step [1]: a compound represented by the following formula (2) as a reaction substrate and a compound represented by the following formula (3) are reacted in the presence of a base to obtain a compound represented by the following formula (4)

Step [2]: The diamine represented by the following formula (6) is obtained by reacting a compound represented by the following formula (4) with amino alcohol (a compound represented by the following formula (5)).

Step [3]: A compound represented by the following formula (1-1) is obtained by reacting a cyclic acid anhydride (a compound represented by the following formula (7)) with the diamine represented by the following formula (6).

(Process [1])

Examples of the compound represented by the formula (2) include halides and derivatives thereof such as benzophenone, 2-naphthylphenyl ketone and bis(2-naphthyl)ketone.

Examples of the compound represented by the formula (3) include hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 1,5-naphthalenediol, and 4,4'-dihydroxyl. Cibiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone , bisphenol A, bisphenol F, bisphenol S, 2,5-dihydroxybiphenyl, and derivatives thereof. Among these, hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4 '-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, and bisphenol A are preferable.

As said derivative, the compound etc. which the substituent couple|bonded with the aromatic hydrocarbon group of the compound represented by the said Formula (2), or the compound represented by Formula (3) are mentioned, for example. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

The amount of the compound represented by the formula (2) and the compound represented by the formula (3) is usually 1 mole or more of the compound represented by the formula (2) with respect to 1 mole of the compound represented by the formula (3), It is preferable to adjust the usage-amount of the compound represented by Formula (2) according to the average degree of polymerization of the molecular chain in a desired sclerosing|hardenable compound. For example, when the average degree of polymerization is 5, 1.2 (1.18 to 1.22) moles of the compound represented by the formula (2) with respect to 1 mole of the compound represented by the formula (3), when the average degree of polymerization is 10, the formula When the compound represented by (2) is 1.1 (1.08 to 1.12) moles and the average degree of polymerization is 20, it is preferable to use about 1.05 (1.04 to 1.06) moles of the compound represented by the formula (2).

In particular, as the compound represented by the formula (2), it is preferable to use at least a halide of benzophenone, and the amount of the halide of benzophenone in the total amount (100 mol%) of the compound represented by the formula (2) Silver is, for example, at least 10 mol%, preferably at least 30 mol%, particularly preferably at least 50 mol% and most preferably at least 80 mol%. In addition, the upper limit is 100 mol%.

In particular, as the compound represented by the formula (3), it is preferable to use at least one compound selected from at least hydroquinone, resorcinol and bisphenol A, and the total amount of the compound represented by the formula (3) (100 The total amount of hydroquinone, resorcinol and bisphenol A in mol%) is, for example, 10 mol% or more, preferably 30 mol% or more, particularly preferably 50 mol% or more, and most preferably 80 mol% or more. In addition, the upper limit is 100 mol%.

The reaction of the compound represented by the formula (2) and the compound represented by the formula (3) is a base (for example, an inorganic base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate; pyridine; , at least one selected from organic bases such as triethylamine). The usage-amount of a base can be suitably adjusted according to the kind of base. For example, when using diacid groups, such as calcium hydroxide, the usage-amount of a base is about 1.0-2.0 mol with respect to 1 mol of the compound represented by Formula (3), for example.

In addition, this reaction can be performed in presence of a solvent. As said solvent, organic solvents, such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, toluene, or these 2 or more types of mixed solvent can be used, for example.

As a usage-amount of the said solvent, it is about 5-20 weight times with respect to the total (weight) of reaction substrates, for example. When the amount of the solvent used exceeds the above range, the concentration of the reaction substrate decreases and the reaction rate tends to decrease.

The reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and for example, any of an air atmosphere, a nitrogen atmosphere, and an argon atmosphere may be used.

Reaction temperature is about 100-200 degreeC, for example. The reaction time is, for example, about 5 to 24 hours. In addition, this reaction can be performed also by any method, such as a batch type, a semi-batch type, and a continuous type.

After completion of this reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization and column chromatography, or a separation means combining these.

(Process [2])

Examples of the compound represented by the formula (5) include 4-aminophenol, 2-amino-6-hydroxynaphthalene, and positional isomers and derivatives thereof.

The usage-amount of the compound represented by said Formula (5) can be suitably adjusted according to the average degree of polymerization of the molecular chain in a desired sclerosing|hardenable compound. For example, in the case of an average degree of polymerization of 5, with respect to 1 mole of the compound represented by Formula (3), in an amount of about 0.4 to 0.6 mole, in the case of an average degree of polymerization of 10, with respect to 1 mole of the compound represented by Formula (3) , 0.2 to about 0.4 mol, and in the case of an average degree of polymerization of 20, it is an amount of about 0.1 to 0.15 mol with respect to 1 mol of the compound represented by Formula (3).

In this reaction, since hydrogen halide is generated as the reaction proceeds, it is preferable to carry out the reaction in the presence of a base that traps the generated hydrogen halide from the viewpoint of obtaining the effect of accelerating the progress of the reaction. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogencarbonate; and organic bases such as pyridine and triethylamine. These can be used individually by 1 type or in combination of 2 or more type.

The amount of the base used can be appropriately adjusted according to the type of the base. For example, when using monoacid bases, such as sodium hydroxide, the usage-amount of a base is about 1.0-3.0 mol with respect to 1 mol of the compound represented by said Formula (5), for example.

In addition, this reaction can be performed in presence of a solvent. As a solvent, the thing similar to that used in process [1] can be used.

Reaction temperature is about 100-200 degreeC, for example. The reaction time is, for example, about 1 to 15 hours. In addition, this reaction can be performed also by any method, such as a batch type, a semi-batch type, and a continuous type.

After completion of this reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization and column chromatography, or a separation means combining these.

(Process [3])

Examples of the cyclic acid anhydride (compound represented by the formula (7)) include maleic anhydride, 2-phenyl maleic anhydride, 4-phenylethynyl-phthalic anhydride, and 4-(1-naphthylethynyl). -phthalic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, derivatives thereof, etc. are mentioned.

The usage-amount of the said cyclic acid anhydride can be suitably adjusted according to the average degree of polymerization of the molecular chain in a desired sclerosing|hardenable compound. For example, in the case of an average degree of polymerization of 5, with respect to 1 mole of the compound represented by Formula (3), an amount of about 0.4 to 0.8 moles, in the case of an average degree of polymerization of 10, with respect to 1 mole of the compound represented by Formula (3) , 0.2 to about 0.4 mol, and in the case of an average degree of polymerization of 20, it is an amount of about 0.1 to 0.15 mol with respect to 1 mol of the compound represented by Formula (3).

This reaction can be carried out in the presence of a solvent. As a solvent, the thing similar to that used in process [1] can be used.

It is preferable to carry out this reaction at room temperature (1-30 degreeC). The reaction time is, for example, about 1 to 30 hours. In addition, this reaction can be performed also by any method, such as a batch type, a semi-batch type, and a continuous type.

In this reaction, azeotroping using a solvent (eg, toluene, etc.) azeotropically with water or using a dehydrating agent (eg, acetic anhydride, etc.) to remove the water produced by the reaction during the reaction , it is preferable from the viewpoint that the progress of the reaction can be accelerated. In addition, it is preferable to perform removal of the product water by a dehydrating agent in presence of a basic catalyst (for example, triethylamine etc.).

After completion of this reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization and column chromatography, or a separation means combining these.

Although the exothermic peak temperature of the curable compound represented by Formula (1) depends on the kind of curable functional group, it is 170-450 degreeC, Preferably it is 200-430 degreeC, Especially preferably, it is 220-420 degreeC. The exothermic peak temperature is determined by DSC measurement.

Since the exothermic peak temperature of the sclerosing|hardenable compound represented by Formula (1) is determined by the kind of sclerosing|hardenable functional group, it is preferable to select a sclerosing|hardenable functional group according to the shaping|molding method employ|adopted. For example, when a curable compound is molded into a film shape by a casting method from a solution dissolved in a solvent and cured, as the curable functional group in the curable compound represented by Formula (1), the above formula (r-5) It is preferable to select a group represented by , and in this case, a cured product can be formed by heating at a temperature of about 250°C. On the other hand, when the group represented by the above formula (r-1) is selected as the curable functional group in the curable compound represented by the formula (1), the curable compound can be melted and molded at a temperature of about 300° C. or less, 380 A hardened|cured material can be formed by heating at the temperature of about degreeC.

In addition, heating may be performed in the state which maintained the temperature constant within the said temperature range, and may change it in stages and may perform it. It is preferable to adjust heating temperature suitably within the said range according to a heating time, For example, when shortening of a heating time is desired, it is preferable to set a heating temperature high. Since the curable compound of the present invention has a structure represented by the above formula (1), it is possible to form a cured product (specifically, a cured product having super heat resistance) without decomposition even when heated at a high temperature, and by heating at high temperature for a short time It is possible to efficiently form a cured product with excellent workability. In addition, there is no restriction|limiting in particular as a heating means, A well-known thru|or a common means can be used.

Hardening of the sclerosing|hardenable compound represented by Formula (1) may be performed under normal pressure, and may be performed under reduced pressure or under pressure.

The 5% weight loss temperature (T _d5 ) of the cured product of the curable compound represented by the formula (1) measured at a temperature increase rate of 10° C./min (in nitrogen) is, for example, 300° C. or higher, more preferably 400° C. or higher, particularly preferably 450°C or higher, and most preferably 500°C or higher. Moreover, an upper limit is 600 degreeC, for example, Preferably it is 550 degreeC, Especially preferably, it is 530 degreeC. In addition, the 5% weight loss temperature can be measured, for example by TG/DTA (differential heat and thermogravimetric simultaneous measurement).

The 10% weight loss temperature (T _d10 ) of the cured product of the curable compound represented by the formula (1) measured at a temperature increase rate of 10° C./min (in nitrogen) is, for example, 300° C. or higher, more preferably 400° C. or higher, particularly preferably 480°C or higher, and most preferably 500°C or higher. Moreover, an upper limit is 600 degreeC, for example, Preferably it is 550 degreeC. In addition, the 10% weight loss temperature can be measured, for example by TG/DTA (differential heat and thermogravimetric simultaneous measurement).

Although the dielectric constant of the hardened|cured material of the curable compound (curable composition) of this invention is not specifically limited, For example, it is preferable that it is 6 or less (for example, 1-6), and it is 5 or less (for example, 1-5). It is more preferable, and it is still more preferable that it is 4 or less (for example, 1-4). In addition, the dielectric loss tangent of the cured product of the curable compound (curable composition) of the present invention is not particularly limited, but for example, it is preferably 0.05 or less (for example, 0.0001 to 0.05), more preferably 0.0001 to 0.03, It is more preferably 0.0001 to 0.015. In addition, the said "permittivity" and "dielectric loss tangent" are a value measured at a measurement frequency of 1 MHz and a measurement temperature of 23 ° C. according to JIS-C2138, or a value measured at a frequency of 1 GHz and 23 ° C. according to ASTM D2520. means

The curable compound of this invention has favorable solvent solubility. Moreover, it can harden|cure rapidly by heat-processing, and can form the hardened|cured material which has super heat resistance as mentioned above. Therefore, it can be used, for example, as a molding material for a composite material used in harsh heat-resistant environments such as electronic information, home appliances, automobiles, and precision machinery, and as a functional material such as an insulating material and a heat-resistant adhesive. In addition, sealing agents, coating agents, adhesives, inks, sealants, resists, forming materials [for example, substrates, electrical insulating materials (insulating films, etc.), laminates, composite materials (fiber-reinforced plastics, prepregs, etc.), optical elements (lenses, etc.) etc.), stereolithography, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, etc.] · It can be preferably used as a sealing agent for covering semiconductor elements in high withstand voltage semiconductor devices (power semiconductors, etc.). Moreover, since the hardened|cured material of the curable compound of this invention has a low dielectric constant and a dielectric loss tangent, it can be used suitably as an insulating material.

[Curable composition]

The curable composition of this invention contains 1 type(s) or 2 or more types of said curable compound, It is characterized by the above-mentioned. The content of the curable compound in the total amount of the curable composition of the present invention (when two or more types are contained, the total amount) is, for example, 30% by weight or more, preferably 50% by weight or more, particularly preferably 70% by weight. % or more, most preferably 90% by weight or more. In addition, the upper limit is 100 weight%. That is, the thing containing only a sclerosing|hardenable compound is included in the curable composition of this invention.

The curable composition of this invention may contain other components other than the said sclerosing|hardenable compound as needed. As other components, well-known or customary additives can be used, for example, curable compounds other than the compound represented by the above formula (1), catalysts, fillers, organic resins (silicone resins, epoxy resins, fluororesins, etc.), solvents, Stabilizers (antioxidants, UV absorbers, light resistance stabilizers, heat stabilizers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant auxiliary agents, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes, plasticizers, mold release agents, and impact resistance modifiers, color modifiers, fluidity modifiers, colorants (dyes, pigments, etc.), dispersants, defoamers, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, and the like. These can be used individually by 1 type or in combination of 2 or more type.

Although the curable composition of the present invention may contain a curable compound other than the curable compound represented by the above formula (1) as the curable compound, the curability represented by the formula (1) in all curable compounds contained in the curable composition The proportion of the compound is, for example, 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more. In addition, the upper limit is 100 weight%.

Further, even if the curable composition of the present invention does not contain a crosslinking agent or a curing accelerator (for example, the total content of the crosslinking agent and curing accelerator in the total amount of the curable composition of the present invention is, for example, 3% by weight or less, preferably Even if it is less than 1 wt%), a cured product can be formed quickly. Therefore, the obtained hardened|cured material has super heat resistance. Moreover, in hardened|cured material, since content of an unreacted hardening accelerator and the decomposition|disassembly product of a hardening accelerator can be suppressed very low, generation|occurrence|production of the outgas derived from these can be suppressed.

Since the curable composition of this invention contains the said sclerosing|hardenable compound, it can harden|cure quickly by heat-processing, and can form the hardened|cured material which has super heat resistance. In addition, heat processing conditions can be set suitably in the range similar to the hardening conditions of the sclerosing|hardenable compound mentioned above.

The curable composition of the present invention is, for example, a molding material or insulation of a composite material (fiber-reinforced plastic, prepreg, etc.) used in harsh heat-resistant environments such as electronic information, home appliances, automobiles, precision machinery, aircraft, and space industrial equipment. It can be suitably used as a functional material, such as a material and a heat-resistant adhesive agent. Others, sealants, paints, inks, sealants, resists, forming materials [automotive parts such as thrust washers, oil filters, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, and pedals; Manufacturing of semiconductors and liquid crystals such as substrates, electrical insulating materials (insulating films, etc.), laminates, electronic papers, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, silicon wafer carriers, IC chip trays, electrolytic capacitor trays, and insulating films device parts; optical parts such as lenses; compressor parts such as pumps, valves, and seals; cabin interior parts of aircraft; Medical device parts, such as a sterilization instrument, a column, and piping, and food/beverage manufacturing equipment parts; It can be preferably used as a housing used for personal computers, mobile phones, etc., and materials for forming members for electric/electronic devices typified by a keyboard support, which is a member for supporting a keyboard inside a personal computer], etc., especially conventional resin materials. It can be preferably used as a sealing agent for covering semiconductor elements in semiconductor devices (power semiconductors, etc.) with high heat resistance and high withstand voltage, which were difficult to cope with. Further, the curable composition of the present invention can be suitably used as an insulating material because its cured product has low dielectric constant and low dielectric loss tangent, and can be particularly suitably used as an interlayer insulating layer in an electric device or an electronic device. have.

[Mold]

The molding of the present invention is characterized in that it contains a cured product obtained by curing the curable composition. Although it does not specifically limit as a formation method of the said molded object, For example, apply|coating and filling a curable composition to a support body, and hardening by heat processing etc. are mentioned. In addition, heat processing conditions can be set suitably in the range similar to the hardening conditions of the sclerosing|hardenable compound mentioned above.

Examples of the molded article of the present invention include composite materials, insulating materials, and heat-resistant adhesives used in harsh heat-resistant environments such as electronic information, home appliances, automobiles, precision machinery, aircraft, and space industrial equipment. Moreover, the semiconductor element in the semiconductor device (power semiconductor etc.) of high heat resistance and high withstand voltage, an electric device, an electronic device, etc. are mentioned.

Example

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

In addition, the measurement was performed under the following conditions.

<NMR measurement>

Measuring device: BRUKER 400MHz/54mm or BRUKER AVANCE 600MHz

Measurement solvent: heavy DMSO, heavy chloroform, or a mixture of heavy chloroform/pentafluorophenol (PFP) = 2/1 (wt/wt)

Chemical shift: TMS as the reference

<GPC measurement>

Apparatus: Pump "LC-20AD" (manufactured by Shimadzu Corporation)

Detector: RID-10A (manufactured by Shimadzu Corporation) or TDA-301 and UV2501 (manufactured by Viscotek)

Solvent: THF or chloroform

Column: shodex GPC KF-801+KF-801+KF-803+KF-806M

Flow rate: 1.0 mL/min

Temperature: 40℃

Sample concentration: 0.1% (wt/vol)

Standard polystyrene equivalent

<DSC measurement>

Device: TA Q20

Temperature increase rate: 10°C/min

Atmosphere: nitrogen atmosphere

<TGA measurement>

Device: NETZSCH TG209F3

Temperature increase rate: 10°C/min

Atmosphere: nitrogen atmosphere

<IR measurement>

Device: Perkin Elmer Spectrum RX1 (ATR method)

Preparation Example 1 (synthesis of diamine-2-1)

Step 1: In a 100 mL (3-neck) flask equipped with a stirring device, a nitrogen introduction tube and a Dean-Stark device, 6.865 g of 4,4'-difluorobenzophenone (4,4'-DFBP), 5.985 g of bisphenol A, 5.427 g of anhydrous potassium carbonate (K ₂ CO ₃ ), 50 mL of N-methylpyrrolidone, and 25 mL of toluene were added, heated while stirring under a nitrogen atmosphere, and toluene was refluxed at 130 to 140° C. for 4 hours. Then, it further heated and toluene was distilled off at 170-180 degreeC. Moreover, after continuing stirring at 170-180 degreeC for 10 hours, it returned to room temperature.

Step 2: To the flask containing the product obtained through Step 1, 1.144 g of 4-aminophenol (4-AP), 1.447 g of anhydrous potassium carbonate, 5 mL of N-methylpyrrolidone and 25 mL of toluene were added, and again under a nitrogen atmosphere. It was heated while stirring, and toluene was refluxed at 130-140 degreeC for 3 hours. Then, it heated and distilled off toluene at 170-180 degreeC, and stirring was continued for 4 hours, maintaining the said temperature. Thereafter, it cooled to room temperature, and the reaction solution was added to 1500 mL of ethanol and filtered to obtain a powdery solid. This powdery solid was repeatedly washed with ethanol and water, and then dried under reduced pressure at 100°C for 8 hours to obtain a powdery solid (diamine-2-1, represented by the following formula (6-1), where n1 is 6.8 compound, yield: 95%).

Preparation Example 2 (Synthesis of diamine-2-2)

In step 1, the usage amount of 4,4'-difluorobenzophenone was changed to 6.586 g, the usage amount of bisphenol A was changed to 6.264 g, and the usage amount of anhydrous potassium carbonate was changed to 5.680 g, and in step 2, 4-aminophenol was Except having changed the usage-amount of 0.599 g and the usage-amount of anhydrous potassium carbonate to 0.599 g, it carried out similarly to Production Example 1, and a powdery solid (diamine-2-2, represented by the said Formula (6-1), where n1 is 9.7, yield: 94%) was obtained.

Preparation 3 (synthesis of diamine-1-1)

Step 1: In a 100 mL (3-neck) flask equipped with a stirring device, a nitrogen introduction tube and a Dean-Stark device, 8.905 g of 4,4'-difluorobenzophenone, 3.745 g of resorcinol, and 7.040 of anhydrous potassium carbonate g, 50 mL of N-methylpyrrolidone and 25 mL of toluene were added, heated while stirring under a nitrogen atmosphere, and toluene was refluxed at 130 to 140°C for 4 hours. Then, it further heated and toluene was distilled off at 170-180 degreeC. Moreover, after continuing stirring at 170-180 degreeC for 10 hours, it returned to room temperature.

Step 2: To the flask containing the product obtained through Step 1, 1.485 g of 4-aminophenol, 1.878 g of anhydrous potassium carbonate, 5 mL of N-methylpyrrolidone, and 25 mL of toluene were added. Again, the mixture was heated while stirring under a nitrogen atmosphere, and toluene was refluxed at 130 to 140°C for 3 hours. Then, it heated and distilled off toluene at 170-180 degreeC, and stirring was continued for 4 hours, maintaining the said temperature. Then, it cooled to room temperature, and obtained the powdery solid by adding and filtering the reaction liquid to 1500 mL of ethanol. This powdery solid was repeatedly washed with ethanol and water, and then dried under reduced pressure at 100°C for 8 hours to obtain a powdery solid (diamine-1-1, represented by the following formula (6-2), where n2 is 6.1 compound, yield: 95%).

Preparation 4 (synthesis of diamine-1-2)

In step 1, the usage-amount of 4,4'-difluorobenzophenone was changed to 9.121 g, the usage-amount of resorcinol was changed to 4.185 g, and the usage-amount of anhydrous potassium carbonate was changed to 7.867 g, in step 2, 4-aminophenol Except for changing the usage-amount of 0.829 g and the usage-amount of anhydrous potassium carbonate to 1.049 g, it carried out similarly to Production Example 3, and a powdery solid (diamine-1-1, represented by the said Formula (6-2), where n2 A compound of 8.8, yield: 93%) was obtained.

¹ H-NMR spectrum and FTIR spectrum of the powdery solid obtained in Preparation Examples 1 to 4 are shown in FIGS. 1 to 6 . In addition, the number average molecular weight, weight average molecular weight, and average polymerization degree calculated|required by gel permeation chromatography (GPC) measurement (solvent THF, standard polystyrene conversion) are shown in the following table|surface.

Example 1 (Synthesis of BEI-2-1)

In a 50 mL (3-neck) flask equipped with a stirring device, a nitrogen introduction tube and a drying tube, 4.550 g of diamine-2-1 obtained in Preparation Example, 1.395 g of 4-phenylethynyl-phthalic anhydride, N-methylpyrroly 33 mL of money was put in, and it stirred at room temperature under nitrogen atmosphere for 18 hours. Thereafter, the drying tube was changed to a Dean-Stark apparatus, 25 mL of toluene was added, and then the temperature was raised to 130 to 140°C, and toluene was refluxed for 5 hours. Then, it heated to 170-180 degreeC, toluene was distilled off, and stirring was continued for 4 hours. Then, it cooled to room temperature, and obtained the powdery solid by adding and filtering the reaction liquid to 1500 mL of ethanol. This powdery solid was washed repeatedly with ethanol and water, and then dried under reduced pressure at 100°C for 8 hours to obtain a powdery solid (BEI-2-1, a compound represented by the following formula (BEI-2), yield: 90%). . ¹ H-NMR spectrum of BEI-2-1 is shown in FIG. 7, and FTIR spectrum is shown in FIG.

¹ H-NMR (CDCl ₃ ) δ: 1.71 (s), 7.02 (m), 7.11 (d, J = 8.8 Hz), 7.21 (d, J = 8.8 Hz), 7.27 (m), 7.41 (m), 7.48(d, J=8.8Hz), 7.58(m), 7.81(m), 7.93(m), 8.08(s)

Example 2 (Synthesis of BEI-2-2)

In the same manner as in Example 1, except that 4.599 g of diamine-2-2 obtained in Production Example and 0.766 g of 4-phenylethynyl-phthalic anhydride were used instead of diamine-2-1, a powdery solid (BEI-2- 2, a compound represented by the above formula (BEI-2), yield: 91%) was obtained. ¹ H-NMR spectrum of BEI-2-2 is shown in FIG. 7, and FTIR spectrum is shown in FIG.

¹ H-NMR (CDCl ₃ ) δ: 1.71 (s), 7.02 (m), 7.11 (d, J = 8.8 Hz), 7.21 (d, J = 8.8 Hz), 7.26 (m), 7.40 (m), 7.48(d, J=8.8Hz), 7.58(m), 7.80(m), 7.93(m), 8.08(s)

Example 3 (Synthesis of BEI-1-1)

In the same manner as in Example 1, except that 4.571 g of diamine-1-1 obtained in Production Example and 1.852 g of 4-phenylethynyl-phthalic anhydride were used instead of diamine-2-1, a powdery solid (BEI-1- 1, a compound represented by the following formula (BEI-1), yield: 90%) was obtained. ¹ H-NMR spectrum of BEI-1-1 is shown in FIG. 10, and FTIR spectrum is shown in FIG.

¹ H-NMR (CDCl ₃ ) δ: 6.83 (m), 6.90 (m), 7.09 (m), 7.21 (d, J = 8.8 Hz), 7.39 (m), 7.48 (d, J = 8.8 Hz), 7.58(m), 7.81(m), 7.92(m), 8.08(s)

Example 4 (Synthesis of BEI-1-2)

Instead of diamine-2-1, it carried out similarly to Example 1, except having used 4.607 g of diamine-1-2 obtained in Production Example and 1.046 g of 4-phenylethynyl-phthalic anhydride, powdery solid (BEI-1- 2, the compound represented by the above formula (BEI-1), yield: 92%) was obtained. The ¹ H-NMR spectrum of BEI-1-2 is shown in FIG. 10 and the FTIR spectrum is shown in FIG. 12 .

¹ H-NMR (CDCl ₃ ) δ: 6.83 (m), 6.90 (m), 7.09 (m), 7.21 (d, J = 8.8 Hz), 7.39 (m), 7.48 (d, J = 8.8 Hz), 7.58(m), 7.81(m), 7.92(m), 8.07(s)

Example 5 (Synthesis of BMI-2-1)

In a 50 mL (3-neck) flask equipped with a stirring device, a nitrogen introduction tube and a drying tube, 4.550 g of diamine-2-1 obtained in Preparation Example, 0.551 g of maleic anhydride, and 33 mL of N-methylpyrrolidone were placed, Under a nitrogen atmosphere, the mixture was stirred at room temperature for 24 hours. Then, 4.215 g of acetic anhydride and 1.405 g of triethylamine were added, and it stirred at 60 degreeC for 6 hours. After returning the reaction solution to room temperature, the reaction solution was added to 1500 mL of ethanol and filtered to obtain a powdery solid. This powdery solid was repeatedly washed with ethanol and water, and then dried under reduced pressure at 100°C for 8 hours to obtain a powdery solid (BMI-2-1, a compound represented by the following formula (BMI-2), yield: 90%). . ¹ H-NMR spectrum of BMI-2-1 is shown in FIG. 13 .

¹ H-NMR(CDCl ₃ )δ: 1.71(s), 6.87(s), 7.02(m), 7.09(m), 7.17(d, J=8.8Hz), 7.26(m), 7.37(d, J) =8.8Hz), 7.80(m)

Example 6 (Synthesis of BMI-1-1)

In the same manner as in Example 5, except that 4.571 g of diamine-1-1 was used instead of diamine-2-1 and the amount of maleic anhydride used was changed to 0.733 g, powdery solid (BMI-1-1, the following formula The compound represented by (BMI-1), yield: 90%) was obtained. ¹ H-NMR spectrum of BMI-1-1 is shown in FIG. 14 .

¹ H-NMR (CDCl ₃ ) δ: 6.88 (m), 7.08 (d, J = 8.0 Hz), 7.17 (d, J = 8.0 Hz), 7.39 (m), 7.81 (d, J = 8.0 Hz)

Example 7 (Synthesis of BMI-1-2)

Step 1: In a 500 mL flask (three-necked) equipped with a stirring device, an argon inlet tube and a Dean-Stark device, 31.443 g of 4,4'-difluorobenzophenone, 13.223 g of resorcinol, 29.894 g of anhydrous potassium carbonate, N -Methylpyrrolidone 180mL and toluene 90mL were put, and it heated while stirring in argon atmosphere, and toluene was refluxed at 130-140 degreeC for 4 hours. Then, it further heated and toluene was distilled off at 170-180 degreeC. Moreover, after continuing stirring at 170-180 degreeC for 10 hours, it returned to room temperature.

Step 2: To the flask containing the product obtained through Step 1, 5.233 g of 4-aminophenol, 6.628 g of anhydrous potassium carbonate, 18 mL of N-methylpyrrolidone and 90 mL of toluene were added, and heated again while stirring under an argon atmosphere, Toluene was refluxed at 130 to 140°C for 3 hours. Then, it heated and distilled off toluene at 170-180 degreeC, and stirring was continued for 4 hours, maintaining the said temperature. Then, it cooled to room temperature, and obtained the powdery solid by adding and filtering the reaction liquid to 5000 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and obtained 37.461g powdery solid (diamine-1-3).

Step 3: 0.878 g of diamine-1-3 obtained in step 2, 4.943 g of maleic anhydride, and 240 mL of N-methylpyrrolidone were put into a 500 mL flask (3 necks) equipped with a stirring device and an argon inlet tube, and argon Under atmosphere, it stirred at room temperature for 18 hours. Then, 8.576 g of acetic anhydride and 0.689 g of sodium acetate were added, and it stirred at 60 degreeC for 6 hours. After returning the reaction liquid to room temperature, powdery solid was obtained by adding the reaction liquid to 5000 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and obtained 28.434g of BMI-1-2. Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-1-2, the polymerization degree calculated from the integrated intensity ratio of signals in ¹ H-NMR spectrum, and Tg obtained by DSC measurement. In addition, ¹ H-NMR spectrum of BMI-1-2 is shown in FIG. 15, IR spectrum is shown in FIG. 46, and DSC measurement result is shown in FIG.

¹ H-NMR (CDCl ₃ /PFP = 2/1) δ: 6.90 (m), 6.98 (d, J = 7.9 Hz), 7.06 (s), 7.10 (s), 7.12 (m), 7.15 (d, 8.3), 7.38 (d, 9.8), 7.47 (dt, J=9.3 Hz, 3.2 Hz), 7.85 (d, J=8.7 Hz)

Example 8 (Synthesis of BMI-2-2)

Step 1: In a 200 mL flask (3 necks) equipped with a stirring device, an argon inlet tube and a Dean-Stark device, 10.476 g of 4,4'-difluorobenzophenone, 9.134 g of bisphenol A, 8.294 g of anhydrous potassium carbonate, N- 60 mL of methylpyrrolidone and 30 mL of toluene were added, heated while stirring in an argon atmosphere, and toluene was refluxed at 130 to 140°C for 4 hours. Then, it further heated and toluene was distilled off at 170-180 degreeC. Moreover, after continuing stirring at 170-180 degreeC for 10 hours, it returned to room temperature.

Step 2: To the flask containing the product obtained through Step 1, 1.744 g of 4-aminophenol, 2.208 g of anhydrous potassium carbonate, 6 mL of N-methylpyrrolidone and 30 mL of toluene were added, and heated again while stirring under an argon atmosphere, Toluene was refluxed at 130 to 140°C for 3 hours. Then, it heated and distilled off toluene at 170-180 degreeC, and stirring was continued for 4 hours, maintaining the said temperature. Then, it cooled to room temperature, and obtained the powdery solid by adding and filtering the reaction liquid to 2000 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and obtained 16.519g powdery solid (diamine-2-3).

Step 3: In a 200 mL flask (3 necks) equipped with a stirring device and an argon inlet tube, 9.100 g of diamine-2-3 obtained in step 2, 1.102 g of maleic anhydride, and 80 mL of N-methylpyrrolidone were put, and argon Under atmosphere, it stirred at room temperature for 18 hours. Then, 1.913 g of acetic anhydride and 0.154 g of sodium acetate were added, and it stirred at 60 degreeC for 6 hours. After returning the reaction liquid to room temperature, powdery solid was obtained by adding the reaction liquid to 1500 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and obtained 8.730g of BMI-2-2. Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-2-2, the polymerization degree calculated from the integrated intensity ratio of signals in ¹ H-NMR spectrum, and Tg obtained by DSC measurement. In addition, ¹ H-NMR spectrum of BMI-2-2 is shown in FIG. 16, IR spectrum is shown in FIG. 47, and DSC measurement result is shown in FIG.

¹ H-NMR (CDCl ₃ ) δ: 1.71 (s), 6.84 (s), 6.99 (d, J = 7.1 Hz), 7.03 (m), 7.07 (d, J = 10.1 Hz), 7.15 (d, J) =8.3Hz), 7.26(d, J=8.3Hz), 7.36(d, J=9.4Hz), 7.78(d, J=7.9Hz), 7.80(d, J=7.9Hz)

Example 9 (Synthesis of BMI-3)

Steps 1 and 2: Using 2,6-naphthalenediol instead of bisphenol A, Table 2 shows the amounts of 2,6-naphthalenediol, 4,4'-difluorobenzophenone and anhydrous potassium carbonate Other than that, 13.533 g of powdery solid (diamine-3) was obtained by performing operation similar to Example 8.

Step 3: The same operation as in Example 8 was performed except that diamine-3 was used instead of diamine-2-3 and the amounts of diamine-3, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 10.854 g of BMI-3 was obtained. The IR spectrum of BMI-3 is shown in FIG. 27, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the polymerization degree calculated from the integral intensity ratio of signals in the ¹ H-NMR spectrum of BMI-3, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-3 is shown in FIG. 17 .

¹ H-NMR(CDCl ₃ )δ: 7.06(s), 7.08(m), 7.13(s), 7.19(m), 7.39(d, J=8.3Hz), 7.84(m)

Example 10 (Synthesis of BMI-4)

Steps 1 and 2: Using 2,7-naphthalenediol instead of bisphenol A, Table 2 shows the amounts of 2,7-naphthalenediol, 4,4'-difluorobenzophenone and anhydrous potassium carbonate Other than that, 14.946 g of powdery solid (diamine-4) was obtained by performing operation similar to Example 8.

Step 3: The same operation as in Example 8 was performed except that diamine-4 was used instead of diamine-2-3 and the amounts of diamine-4, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 12.457 g of BMI-4 was obtained. The IR spectrum of BMI-4 is shown in FIG. 28, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-4, the polymerization degree calculated from the integrated intensity ratio of signals of ¹ H-NMR spectrum, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-4 is shown in FIG. 18 .

¹ H-NMR (CDCl ₃ /PFP = 2/1) δ: 7.05 (s), 7.11 (d, J = 8.7 Hz), 7.16 (d, J = 9.6 Hz), 7.17 (d, J = 7.9 Hz) , 7.27(d, J=7.2Hz), 7.38(d, J=8.7Hz), 7.43(s), 7.88(d, J=9.1Hz), 7.93(d, J=8.3Hz)

Example 11 (Synthesis of BMI-5)

Steps 1 and 2: Using 4,4'-dihydroxydiphenyl ether instead of bisphenol A, 4,4'-dihydroxydiphenyl ether, 4,4'-difluorobenzophenone and anhydrous potassium carbonate 14.787 g of powdery solid (diamine-5) was obtained by performing operation similar to Example 8 except having made the usage-amount into Table 2 being shown.

Step 3: The same operation as in Example 8 was performed except that diamine-5 was used instead of diamine-2-3 and the amounts of diamine-5, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 12.468 g of BMI-5 was obtained. The IR spectrum of BMI-5 is shown in FIG. 29, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the polymerization degree calculated from the integral intensity ratio of signals in the ¹ H-NMR spectrum of BMI-5, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-5 is shown in FIG. 19 .

¹ H-NMR (CDCl ₃ /PFP = 2/1) δ: 7.06 (s), 7.11 (d, J = 10.1 Hz), 7.16 (d, J = 9.4 Hz), 7.21 (m), 7.34 (d, J=9.4Hz), 7.55(s), 7.87(m), 7.89(m)

Example 12 (Synthesis of BMI-6)

Steps 1 and 2: Using 4,4'-dihydroxybenzophenone instead of bisphenol A, the amount of 4,4'-dihydroxybenzophenone, 4,4'-difluorobenzophenone and anhydrous potassium carbonate 13.602 g of powdery solid (diamine-6) was obtained by performing the same operation as in Example 8, except having shown in Table 2.

Step 3: The same operation as in Example 8 was performed except that diamine-6 was used instead of diamine-2-3 and the amounts of diamine-6, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 10.435 g of BMI-6 was obtained. The IR spectrum of BMI-6 is shown in FIG. 30, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the polymerization degree calculated from the integral intensity ratio of signals in the ¹ H-NMR spectrum of BMI-6, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-6 is shown in FIG. 20 .

¹ H-NMR (CDCl ₃ /PFP = 2/1) δ: 7.07 (s), 7.23 (d, J = 9.4 Hz), 7.32 (d, J = 7.6 Hz), 7.40 (d, J = 8.3 Hz) , 7.91(m), 7.95(d, J=8.6Hz)

Example 13 (Synthesis of BMI-7)

Steps 1 and 2: Using 4,4'-dihydroxydiphenylsulfone instead of bisphenol A, 4,4'-dihydroxydiphenylsulfone, 4,4'-difluorobenzophenone and anhydrous potassium carbonate 14.118 g of powdery solid (diamine-7) was obtained by performing the same operation as in Example 8 except that the usage-amount was shown in Table 2.

Step 3: The same operation as in Example 8 was performed except that diamine-7 was used instead of diamine-2-3 and the amounts of diamine-7, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 10.724 g of BMI-7 was obtained. The IR spectrum of BMI-7 is shown in FIG. 31, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-7, the polymerization degree calculated from the integrated intensity ratio of the signal of ¹ H-NMR spectrum, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-7 is shown in FIG. 21 .

¹ H-NMR (CDCl ₃ ) δ: 6.88 (s), 7.11 (d, J = 8.3 Hz), 7.14 (d, J = 9.4 Hz), 7.24 (d, J = 8.3 Hz), 7.38 (d, J) =8.3Hz), 7.85(m), 7.94(d, J=8.6Hz)

Example 14 (Synthesis of BMI-8)

Steps 1 and 2: Using 4,4'-dihydroxydiphenyl sulfide instead of bisphenol A, 4,4'-dihydroxydiphenyl sulfide, 4,4'-difluorobenzophenone and anhydrous 17.041 g of powdery solid (diamine-8) was obtained by performing operation similar to Example 8 except having made the usage-amount of potassium carbonate into Table 2 being shown.

Step 3: The same operation as in Example 8 was performed except that diamine-8 was used instead of diamine-2-3 and the amounts of diamine-8, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 13.303 g of BMI-8 was obtained. The IR spectrum of BMI-8 is shown in FIG. 32, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the polymerization degree calculated from the integral intensity ratio of signals of the ¹ H-NMR spectrum of BMI-8, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-8 is shown in FIG. 22 .

¹ H-NMR (CDCl ₃ /PFP = 2/1) δ: 7.06 (s), 7.09 (d, J = 9.4 Hz), 7.10 (d, J = 9.4 Hz), 7.17 (m), 7.31 (m) , 7.45 (d, J=8.3 Hz), 7.85 (d, J=8.3 Hz)

Example 15 (Synthesis of BMI-9)

Steps 1 and 2: Using a mixture of resorcinol and hydroquinone (molar ratio of the former to the latter of 4:1) instead of bisphenol A, the mixture, 4,4'-difluorobenzophenone and anhydrous potassium carbonate 11.408 g of powdery solid (diamine-9) was obtained by performing the same operation as in Example 8 except that the usage-amount was shown in Table 2.

Step 3: The same operation as in Example 8 was performed except that diamine-9 was used instead of diamine-2-3 and the amounts of diamine-9, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 7.109 g of BMI-9 was obtained. The IR spectrum of BMI-9 is shown in FIG. 33, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-9, the polymerization degree calculated from the integrated intensity ratio of signals of ¹ H-NMR spectrum, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-9 is shown in FIG. 23 .

¹ H-NMR (CDCl ₃ ) δ: 6.63 (s), 6.85 (s), 6.90 (d, J = 7.3 Hz), 7.07 (m), 7.12 (m), 7.14 (d, J = 7.9 Hz), 7.37(d, J=9.4Hz), 7.80(m)

Example 16 (Synthesis of BMI-10)

Steps 1 and 2: Using a mixture of resorcinol and 4,4'-dihydroxybiphenyl (molar ratio of the former and the latter of 4:1) instead of bisphenol A, the mixture, 4,4'-di 12.073 g of a powdery solid (diamine-10) was obtained by performing the same operation as in Example 8 except that the usage-amounts of fluorobenzophenone and anhydrous potassium carbonate were shown in Table 2.

Step 3: The same operation as in Example 8 was performed except that diamine-10 was used instead of diamine-2-3 and the amounts of diamine-10, maleic anhydride, acetic anhydride and sodium acetate used were shown in Table 3, 8.695 g of BMI-10 was obtained. The IR spectrum of BMI-10 is shown in FIG. 34, and the DSC measurement result is shown in FIG. In addition, Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-10, the polymerization degree calculated from the integrated intensity ratio of signals of ¹ H-NMR spectrum, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-10 is shown in FIG. 24 .

¹ H-NMR (CDCl ₃ /PFP = 2/1) δ: 6.91 (m), 6.97 (m), 7.06 (s), 7.11 (d, J = 9.4 Hz), 7.13 (d, J = 7.6 Hz) , 7.18(d, J=8.7Hz), 7.20(d, J=7.6Hz), 7.39(d, J=9.1Hz), 7.47 (t, J=7.9Hz), 7.67(d, J=7.6Hz) , 7.86 (d, J=9.4 Hz)

Example 17 (Synthesis of BMI-1-3)

Steps 1 and 2: 12.630 g of powdery solid ( diamine-1-4) was obtained.

Step 3: 10.293 g of diamine-1-4 obtained in step 2, 1.648 g of maleic anhydride, 80 mL of N-methylpyrrolidone in a 200 mL flask (3 neck) equipped with a stirring device, an argon inlet tube and a Dean-Stark device And 60 mL of toluene was added, and it stirred at room temperature under argon atmosphere for 18 hours. Thereafter, 0.107 g of p-toluenesulfonic acid (pTSA) was added, the temperature was raised to 140°C, and stirring was continued for 8 hours, and toluene was refluxed to remove water. After returning the reaction liquid to room temperature, powdery solid was obtained by adding the reaction liquid to 1500 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and obtained 9.320 g of BMI-1-3. Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-1-3, the polymerization degree calculated from the integrated intensity ratio of signals of ¹ H-NMR spectrum, and Tg obtained by DSC measurement. In addition, ¹ H-NMR spectrum of BMI-1-3 is shown in FIG.

¹ H-NMR (CDCl ₃ /PFP = 2/1) δ: 6.90 (m), 6.96 (d, J = 7.9 Hz), 7.05 (s), 7.10 (s), 7.12 (m), 7.13 (d, 8.3), 7.38 (d, 9.8), 7.46 (dt, J=9.3 Hz, 3.2 Hz), 7.85 (d, J=8.7 Hz)

Example 18 (Synthesis of BMI-1-4)

Steps 1 and 2: 12.639 g of powdery solid ( diamine-1-5) was obtained.

Step 3: 10.293 g of diamine-1-5 obtained in step 2, 1.648 g of maleic anhydride, 80 mL of N-methylpyrrolidone in a 200 mL flask (3 neck) equipped with a stirring device, an argon inlet tube, and a Dean-Stark device And 60 mL of toluene was added, and it stirred at room temperature under argon atmosphere for 18 hours. Thereafter, 0.528 g of pyridinium p-toluenesulfonate (PPTS) was added, and the temperature was raised to 140° C., stirring was continued for 6 hours, and toluene was refluxed to remove moisture. After returning the reaction liquid to room temperature, powdery solid was obtained by adding the reaction liquid to 1500 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and obtained 9.801g of BMI-1-4. Table 4 shows the number average molecular weight and polymerization degree calculated by GPC measurement of BMI-1-4, the polymerization degree calculated from the integrated intensity ratio of signals of ¹ H-NMR spectrum, and Tg obtained by DSC measurement. Also, ¹ H-NMR spectrum of BMI-1-4 is shown in FIG. 26 .

¹ H-NMR (CDCl ₃ ) δ: 6.82 (s), 6.87 (s), 6.90 (d, J = 8.7 Hz), 7.08 (d, J = 7.8 Hz), 7.17 (d, J = 8.7 Hz), 7.38(m), 7.81(d, J=7.8Hz)

In Table 4, "-" represents that which was not implemented.

evaluation

Tg and exothermic peak temperature of the samples obtained in Examples 1 to 4 were determined by DSC measurement. The results are shown in FIG. 43 . BEI-2-1 and BEI-2-2 have a Tg of about 140°C, BEI-1-1 and BEI-1-2 have a Tg of about 120°C, and BEI-2-1 and BEI-2-2 , BEI-1-1, and BEI-1-2 all showed exothermic peaks due to curing reaction around 400°C.

The samples (0.1 g) obtained in Examples 1 to 6 and 9 to 16 were mixed with a solvent (10 g) shown in Table 5 below, and stirred at room temperature, 50°C, and 100°C for 24 hours. When the powdery solid was dissolved at 50° C. or lower, it was evaluated as having good solubility in solvent (◎), when it was dissolved at 100° C., as having good solubility (○), and when it was insoluble at 100° C., it was evaluated as having poor solubility in solvent (×). In addition, "-" represents that it is not implemented.

NMP: N-methyl-2-pyrrolidone

DMSO: dimethyl sulfoxide

THF: tetrahydrofuran

The samples obtained in Examples 1 to 6 and 9 to 16 were placed on a glass plate so as to be uniform in thickness of about 0.5 mm, and cured by heating in a muffle furnace. In the muffle furnace, the temperature was raised from 25°C to 371°C at 10°C/min, and then held at 371°C for 2 hours. 44 shows the DSC result of the cured product obtained from the samples of Examples 1 to 6, and FIG. 45 shows the thermogravimetric reduction analysis result. In addition, Table 6 shows the 5% weight loss temperature (T _d5 ) and the 10% weight loss temperature (T _d10 ) of the cured products obtained from the samples of Examples 1 to 6 and 9 to 16 .

Since the exothermic peak is not seen in the DSC chart of FIG. 44, it can be seen that the compounds obtained in Examples 1 to 4 have excellent curability (all curable functional groups are lost due to curing). 45, T _d5 of the hardened|cured material of the compound obtained in Examples 1-4 were all 500 degreeC or more.

The viscosity (200°C) of BMI-1-2 was measured with a rheometer and found to be 180000 mPa·s.

BMI-1-2 was cured by vacuum compression molding to obtain a cured product. Specifically, the mold for molding into which BMI-1-2 was put was set on a press machine (30 ton manual hydraulic vacuum capable hot press IMC-46E2-3 type, manufactured by Imotto Seisakusho), adjusted to 50°C, and vacuum While heating, the temperature was raised to 220°C at 20°C/min and held for 1 hour, then the press machine was air cooled and water cooled, and the mold was taken out from the portion at 100°C or lower to obtain a cured product. In addition, the molding pressure at the time of temperature increase of 50 degreeC - 220 degreeC was 70-80 kgf/cm<2>, and the shaping|molding pressure at the time of holding|maintaining at 220 degreeC was 200-250 kgf/cm<2>. The physical properties of the obtained cured product are described below.

·Density (JIS K7112A 23℃): 1.30g/cm3

·Glass transition temperature (measured by DSC): 150°C

·Coefficient of thermal expansion (according to JIS K7197) (Tg or less): 45 ppm/°C

·Coefficient of thermal expansion (according to JIS K7197) (Tg or more): 185 ppm/°C

· Specific permittivity (23°C according to JIS-C2138) (1 MHz): 3.54

Specific dielectric constant (23°C according to ASTM D2520) (1 GHz): 3.18

Dielectric loss tangent (23°C according to JIS-C2138) (1 MHz): 0.0067

Dielectric loss tangent (23°C according to ASTM D2520) (1 GHz): 0.0054

The curable compound of this invention has favorable solvent solubility. Moreover, it can harden|cure quickly by heat-processing, and can form the hardened|cured material which has super heat resistance. Therefore, it can be used suitably as a sealing agent etc. of a semiconductor device.

Claims (12)

A sclerosing|hardenable compound represented by following formula (1).

[wherein, R ¹ , R ² are the same or different, and represent a curable functional group having a cyclic imide structure, and D ¹ , D ² are a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imide bond. represents a 1,4-phenylene group which may have at least one group selected from the group consisting of a de bond. L represents a divalent group represented by the following formula (I-1).

(Wherein, Ar ¹ to Ar ³ are the same or different, and a group excluding two hydrogen atoms from the structural formula of an aromatic ring, or a group excluding two hydrogen atoms from a structural formula in which two or more aromatic rings are bonded through a single bond or a linking group The linking group is a divalent hydrocarbon group having 1 to 5 carbon atoms or a group in which at least one hydrogen atom of a divalent hydrocarbon group having 1 to 5 carbon atoms is substituted with a halogen atom. X is -CO-, -S- or - represents SO ₂ -, Y is the same or different, and represents -S-, -SO ₂ -, -O-, -CO-, -COO- or -CONH-. n represents an integer of 0 or more. m1 represents 3 to 40.)] The curable compound according to claim 1, wherein R ¹ and R ² in formula (1) are the same or different and are selected from groups represented by the following formulas (r-1) to (r-6).

(In the formula, a bond extending from a nitrogen atom bonds with D ¹ or D ² ) The group according to claim 1 or 2, wherein Ar ¹ to Ar ³ in formula (I-1) are the same or different, and excluding two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms, or a group having 6 to 14 carbon atoms. At least two of the aromatic rings of 14 are a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or at least one hydrogen atom in a linear or branched alkylene group having 1 to 5 carbon atoms is substituted with a halogen atom A curable compound that is a group excluding two hydrogen atoms from the structural formula bonded through the group. The curable compound according to claim 1 or 2, wherein the structure represented by the following formula (I) in the formula (I-1) is a structure derived from benzophenone.

The curable compound according to claim 4, wherein the proportion of the structural unit derived from benzophenone in the total amount of the curable compound represented by the formula (1) is 5% by weight or more. The structure according to claim 1 or 2, wherein the structure represented by the following formula (II) in the formula (I-1) is hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4 , 4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4' - A curable compound having a structure derived from at least one compound selected from dihydroxydiphenylsulfone and bisphenol A.

The curable compound according to claim 6, wherein the proportion of structural units derived from hydroquinone, resorcinol and bisphenol A in the total amount of the curable compound represented by formula (1) is 5 wt% or more. A curable composition comprising the curable compound according to claim 1 or 2. A cured product of the curable composition according to claim 8. A molded product comprising the cured product according to claim 9 . delete delete

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